CS245172B1 - Mixed explosive - Google Patents

Abstract

The solution relates to a mixed explosive with an oxygen donor of the nitrate and/or perchlorate type, which contains 0.5 to 10% by weight of distillation residues from the production of cyclohexanone from benzene, calculated on the weight of the resulting mixture. The process, or rather the explosive according to the invention, is important both for the efficiency of the production of cyclohexanone and for the separation of rocks.

Description

245172 2

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blasting explosive with an oxygen donor of the nitrate and / or perchlorate type, comprising distillates from the production of cyclohexanone from benzene. The importance of mixed explosives is increasing in both civilian and military applications. Ammonium nitrate - the most common blend of ammonium nitrate blasting agents - is the most widely used oxygen donor, consisting of two main groups: I. ammonium nitrate mixtures with fuel; II. mixtures of ammonium nitrate, water with a plasticizer additive, and a substance of explosive nature, or a sensitizer.

The first group explosives can be produced by stable technological equipment, but their production is more frequent on the ground. in mobile mixing devices or directly in boreholes /.

Ammonium nitrate is mixed with a fuel that can be a wide variety of organic pigments, but paraffins, fuel oils, and diesel are most commonly used. These blends have an approximate zero oxygen balance, corresponding to 94% by weight. ammonium nitrate and 6 wt. diesel or fuel oil in explosives; said fuel content will increase the explosive heat value from 1,470 kJ / kg 1 for ammonium nitrate up to 3,738 kJ / kg, which is proportional to the increase in working capacity of the explosive compared to ammonium nitrate alone.

Explosives of this type are known in the Czech Republic under the code name DAP, abroad they are similarly referred to as ANDK / in NDR /, ANC / in NSR /, Igdanite / in USSR /, ANFO or AŇBA in Anglo-American literature. When the fuel is coal dust, metal powder, and the like, these mixtures are also referred to as nitric carbonates and designated NCNs.

Amonoliad explosives of the second group, characterized by relatively simple and inexpensive production technology. We are known under the name TPV / water plasticized explosives in the United States and Canada for slurry Explosives, which is currently the most explosive distribution of this type according to sensitization to: a / "Slury Explosives" / code SE / which is sensitized by an explosive additive / trinitrotoluene, hexogen, nitroesters, nitrates, alkanol- or alkylamines, hydroxialkyl-nitrates and the like /; (b) "Slurry Blasting Agents", which do not contain explosive additives and asensitized non-explosive components, most commonly aluminum dust / eg Soviet Aquarium (s) and / or other substance / fuel oil, fibrous cellulose, polyvinyl chloride dust, sulfur, paraffin, hexamethylenetetramine, polyols, sugars and others / 4 respectively aerated / expanded perlite , glass pulp, glass hollow spheres, cork, polystyrene, ammonium nitrate, etc., or substances gas / peroxides, nitrites, carbonates, 1,5-endomethylene-3,7-dinitroso-1,3,5,7-tetraazacycloctane and others.

The stability of physical stability, that is to say, the separation of the constituents of these "Slurry" subsets of explosives while maintaining flowability or plasticity of the composition is ensured by the addition of a gelling agent / plasticizer (such as guar gum) and its alkylated derivatives, polyvinyl alcohol, sodium or ammonium salts of carboximethylcellulose, oxiethylcellulose, polyacrylamide and others.

The youngest type of "Slurry" explosive is a water-in-oil emulsion composition, coded W / O, or an oil-in-water emulsion, code-named 0 / W; the production of compositions W / O consists in introducing aqueous solutions of blasting components into the hydrophobic liquid / fuel oil and the like / and the opposite is done in the production of O / W compositions. 3 245172

These emulsions are stabilized with dispersants, such as fatty acid salts (fatty acid or oily), fatty acid esters (e.g. deca glycerol decaeate, deca-glycerin deca stearate /, partially esterified with polyols by fatty acids (e.g. mono-stearate, monooleate, monopalmitate or sorbitol tristerate, mono- or diglycerides of fatty acid fatty acids (furthermore alkylphenylsulfonates, soybean lecithin, oxyethyleneoxypropylene copolymer and others). Emulsion explosives can be sensitized by nitro compounds, most commonly nitromethane or other nitroparafins, but in technical practice the most widely used is their sensitization by aerating agents or gas-releasing additives. Calcium nitrate and sodium perchlorate are sometimes also used as oxygen donors in "slurry" explosives, the latter being mainly in aluminized compositions. However, the low production costs, the high safety of handling and the actual production and the possibility of the mechanization of the blasting machine are, in particular, characterized by explosive compositions based on ammonium nitrate.

This is the main reason why, in technical practice, the exploitation of mixed explosives such as DAP, «PV» and now even W / 0 and 0 / W predominate over the exploding of other types of industrial explosives.

An analogous trend in the field of explosives for military purposes (aluminized aqueous ammonium nitrate gels, for example, is directed to some types of air bombs, trinitroluene is replaced by liquid compositions based on aqueous solutions of hydrazine nitrate and the like).

Many of the components of mixed explosives find themselves more significant and economically more attractive in vigorous sectors of the national economy (eg. diesel, fuel oil and others /; on the other hand, the application of some traditional toxicological and / or safety densitizers (trinitrotoluene and nitroesters) is abandoned.

The gap thus formed can be filled with suitable, especially by-products of the chemical industry, the further processing of which is still important.

According to the present invention, the mixed explosive with oxygen donors of the nitrate and / or perchlorate type is produced with a content of 0.5 to 10% by weight. distillation residues of the production of cyclohexanone from benzene, calculated on the weight of the resulting composition. An advantage of the process of the present invention is the technical and economical availability of distillation residues from the production of cyclohexanone, which in a continuous process from benzene represents a liquid mixture of polymeric cycloaliphatic compounds with a boiling point of about 150 ° C and relatively constant other physico-chemical characteristics. The use in accordance with this invention of the distillation residues of the production of cyclohexanone from benzene contributes to increasing the economic efficiency of this production.

Application of the mentioned residues in the production of intermediate products and products of the explosive technology led to the saving of motor oil, fuel oil and other noble products of petrochemical technologies, so far applied as fuels and sensitizers of mixed explosives, while retaining the properties of the resulting explosives.

Explosives containing distillation residues of cyclohexanone from benzene are aluminizable. Their physical stability can be increased by conventional means, e.g. in the case of DAPge type explosives, the application of adherent ammonium nitrate and / or the addition of wood flour and / or other suitable adsorbent / water-soluble urea-formaldehyde powder condensate, modified fine-grained silica and the like. in the case of explosives of the TPV type, it is a suitable gelling agent and, in the case of W / O or O / W type explosives, a suitable dispersant.

However, the stabilizer here may also be nitrocellulose which swells in the cyclohexanone benzene residue from being slightly gelatinized. 245172 4

The application of the present invention to the distillation residues of the production of cyclohexanone from benzene has not yet been described in the literature; the mixed explosive resulting from this application is documented by the following examples, which in no way exclude the variability of the process of the invention. A rt 1 'a d 1 Available! distillation residues of the production of cyclohexanone from benzene with a content of 4.9% by weight of cyclohexanol, a specific gravity of 970 kg.m-3 at 20 ° C, with a flash point of 110 ° C and a temperature of 150 ° C at a pressure of 6.7 kPa, of viscosity 36.10 3 Ps.s at 60 ° C, holding at 10 ° C honey, at -20 ° C asphalt consistency and full solid at -60 ° C. The calorific value of these residues is 38,100 kJ kg -1. From the mentioned ammonium nitrate and technical nitrate, a semi-particulate composition (% w / w: 7.1% distillation residues, 0.98% water and 91.92% ammonium nitrate) is prepared at atmospheric pressure. This mixture is approximate zero oxygen balance and for mernd charge weight of 1,100 kg.m 3 is characterized by data: max. Explosion heat /kJ.kg 1/770 full ideal explosion work / kJ.kg-1 / 3.090 volume of explosion outflows / l.kg-1/960 detonation rate /km.s 1 / 2.3 to 2.6 Example 2 A black powder type composition of composition /% is prepared from the distillation residue of Example 1, sodium nitrate, powdered sulfur and wood pulp. 77.2 L of nitrate, 7.9% of sulfur, 8.1 and distillation residues, and 6.8% of wood pulp. The mixture has the following characteristics: oxygen bilanoia /% / max. Explosion heat / kJ.kg 1 / full ideal explosion work /kJ.kg 1 / volume of explosion fumes / l.kg 1 / grain density / kg.m / _ 3 bulk density /kg.m / detonation speed /km.s 1 / -8.73 7302 700 360 1 550 to 970 2.2 to 2, 1 650 Example 3

A mixture of 2,4,6-tr initrotoluene, aluminum dust having a specific surface area of about 0.7 m sodium sulphate, a gelling agent of guar gum and distillation residues is introduced into a 68.9% aqueous ammonium nitrate solution in a malaxer on a cycle. from Example 1. The homogenization results in a mixed explosive of composition /% w / w: 31.9% trinitrotoluene, 9.5% aluminum, 22.5% sodium nitrate, 23.9% ammonium nitrate, 10.2% water, 1, 4% distillation residues and 0.6% guar gum. Water produced in this way plasticized explosive mánasled next characteristics: oxygen balance /% / -29.1 max. Explosion heat /kJ.kg 1 / 4.875 complete ideal work of explosion /kJ.kg 3,500 volume of explosion flue gases /l.kg 1/630 specific gravity grains / kg.m ^ / 1,400 to 1,450 detonation rate / km.s 1 / 4.3 to 4.5

Claims (1)

No. 5,251,572 Example 4 927 wt. parts of the cyclohexanone production of Example 1 are poured onto the present 75.7% by weight. parts of dewatered nitrocellulose containing 30 wt. ethyl alcohol, characterized by a content of 12.6 wt. nitrogen in dry matter. The swollen nitrocellulose is introduced into the present 8,670 wt. parts of 2,4,6-trinitrotoluene 90 to 95 ° C warm, placed in a heated malaxier. After a 10-minute homogenization and withdrawal in nitrocellulose of the ethyl alcohol contained therein, the kneader content is deposited in a thin sheet of aluminum sheets. After the melt has cooled, it can be used in the manufacture of mixed explosives. Using differential thermal analysis (DTA), operating at a temperature rise rate of 5 ° C min -1 and a measurement range of 1 mV per scale scale, the starting nitrocellulose was found to be the beginning of exothermic decomposition at 153.5 ° C. In an analogous manner, the melting point at 79.6 ° C, the melting peak at 81.8 ° C and the beginning of the exothermic solution at 148.5 ° C were solidified. EXAMPLE 5 From the melt of Example 4, ammonium nitrate, sodium nitrate and ammonium perchlorate, a mixture of the composition (% by weight: 37.4% ammonium nitrate, 15.9% sodium nitrate, 22.1% ammonium perchlorate) was prepared in a cycle. , 21.3% trinitrotoluene, 2.3% residual 1% nitrocellulose. This mixture is characterized by data: oxygen balance /% / +0.8 max. Explosion heat /kJ.kg J / 4 822 complete ideal explosion work /kJ.kg V 3 600 explosion volume of combustion products / l.kg 1/740 WEEK Τ BACKGROUND OF THE INVENTION A mixed oxygen donor of nitrate and / or perchlorate type, characterized in that it contains 0.5 to 10% by weight, preferably 1.4 to 9.27% by weight. distillation residues from the production of cyclohexanone from benzene, calculated on the weight of the resulting mixture.